US2872485A - Process - Google Patents
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- Publication number
- US2872485A US2872485A US610643A US61064356A US2872485A US 2872485 A US2872485 A US 2872485A US 610643 A US610643 A US 610643A US 61064356 A US61064356 A US 61064356A US 2872485 A US2872485 A US 2872485A
- Authority
- US
- United States
- Prior art keywords
- diformylhydrazine
- dihydrazone
- triazine
- reaction
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
Definitions
- All diluents and reactants are preferably anhydrous. Since the reaction product tends to turn pink or red in light, it is advantageous to carry out the reaction in the dark. This contamination, however, can be easily removed by washing the crude diformylhydrazine dihydrazone with ether or petroleum ether, or by briefly exposing the product to a vacuum. Since diformylhydrazine dihydrazone is easily oxidized, better results are obtained if the reaction is carried out in a non-oxidizing atmosphere, for instance as under hydrogen or nitrogen.
- Diformylhydrazine dihydrazone is a useful intermediate for the preparation of 1,2,4-triazole and amino- 1,2,4-triazole, the latter being known as an excellent herbicide.
- 1,3,5-triazine can be prepared by reacting hydrochloric acid with hydrocyanic acid and treating the resulting compound with a dehydrohalogenating agent, for example, quinoline.
- a dehydrohalogenating agent for example, quinoline.
- This material was further purified by digestion with 5 milliliters of cold absolute alcohol for 30 minutes followed by rapid filtration under a nitrogen atmosphere. About 4.8 grams of pure diformylhydrazine dihydrazone, which melted at 122-123 C. with decomposition, was obtained.
- the method of preparing diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine at a temperature of about 0 to 40 C.
- diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine at a temperature of about 0 to 40 C. and in the presence of an inert organic diluent.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United PROCESS Christoph J. Grundmann and Alfred Kreutzberger, Co-
lumbus, Ohio, assignors to Olin Mathieson Chemical Corporation, a corporation of Virginia Application September 18, 1956 Serial No. 610,643
6 Claims. (Cl. 260-564) No Drawing.
rates Patent According to our invention, 1,3,5-triazine .is reacted with anhydrous hydrazine, preferably at a temperature from 0 to 40 C., until no more ammonia is evolved. This takes usually from 3 to 12 hours. The reaction is easily carried out by simply admixing the reactants. Because this reaction evolves heat rapidly, even at room temperature, it is preferably carried out in a suitable inert diluent. Such solvents include, for example, the lower aliphatic alcohols as methanol, ethanol, isopropanol and t-butanol, and other solvents such as diethyl ether, tetrahydrofuran and dioxane. All diluents and reactants are preferably anhydrous. Since the reaction product tends to turn pink or red in light, it is advantageous to carry out the reaction in the dark. This contamination, however, can be easily removed by washing the crude diformylhydrazine dihydrazone with ether or petroleum ether, or by briefly exposing the product to a vacuum. Since diformylhydrazine dihydrazone is easily oxidized, better results are obtained if the reaction is carried out in a non-oxidizing atmosphere, for instance as under hydrogen or nitrogen.
Diformylhydrazine dihydrazone is a useful intermedi ate for the preparation of 1,2,4-triazole and amino- 1,2,4-triazole, the latter being known as an excellent herbicide.
1,3,5-triazine can be prepared by reacting hydrochloric acid with hydrocyanic acid and treating the resulting compound with a dehydrohalogenating agent, for example, quinoline.
The following example further illustrates this invention:
"ice
To an ice-cooled solution of 3 grams of 1,3,5-triazine in 25 milliliters of anhydrous ether there was added dropwise 5.3 grams of anhydrous hydrazine. During this time, a white solid precipitated, and gaseous ammonia escaped from the reaction mixture. After allowing the reaction mixture to stand for 12 hours at room temperature, the precipitate was filtered by vacuum, washed with 10 milliliters of cold ether and dried over phosphorus pentoxide in a vacuum for 2 hours. The diformylhydrazine dihydrazone so obtained, was a yellowish microcrystalline powder which melted at ll71l8 C. The yield Was 5.3 grams or 79 percent of the theory.
This material was further purified by digestion with 5 milliliters of cold absolute alcohol for 30 minutes followed by rapid filtration under a nitrogen atmosphere. About 4.8 grams of pure diformylhydrazine dihydrazone, which melted at 122-123 C. with decomposition, was obtained.
Calculated for CgHsNa 20. 68 6. 72. 37 Found 21. 00 7.09 72. 20
The following table indicates the yields which were obtained when the procedure of the first paragraph of this example was duplicated except that the various solvents listed below were used instead of the ether solvent.
1. The method of preparing diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine.
2. The method of preparing diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine at a temperature of about 0 to 40 C.
3. The method of preparing diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine in the presence of an inert organic diluent.
4. The method of preparing diformylhydrazine dihydrazone which comprises admixing 1,3,5-triazine with anhydrous hydrazine at a temperature of about 0 to 40 C. and in the presence of an inert organic diluent.
5. The method of claim 1 in which the reaction is carried out in a non-oxidizing atmosphere.
6. The method of claim 4 in which the reaction is carried out in a non-oxidizing atmosphere.
References Cited in the file of this patent Muller et al.: Chem. Abst., vol. 15, pages 3849-S0 (1921).
Grundmann et al.: J. A. C. S. 76, 5646-50 (1954).
Claims (1)
1. THE METHOD OF PREPARING DIFORMYLHYDRAZINE DIHLDRAZONE WHICH COMPRISES ADMIXING 1,3,5,-TRIAZINE WITH ANHYDROUS HYDRAINE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US610643A US2872485A (en) | 1956-09-18 | 1956-09-18 | Process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US610643A US2872485A (en) | 1956-09-18 | 1956-09-18 | Process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2872485A true US2872485A (en) | 1959-02-03 |
Family
ID=24445862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US610643A Expired - Lifetime US2872485A (en) | 1956-09-18 | 1956-09-18 | Process |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2872485A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3211746A (en) * | 1962-04-03 | 1965-10-12 | Ciba Geigy Corp | Guanylhydrazones of biguanidoarylketones |
-
1956
- 1956-09-18 US US610643A patent/US2872485A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3211746A (en) * | 1962-04-03 | 1965-10-12 | Ciba Geigy Corp | Guanylhydrazones of biguanidoarylketones |
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